U.S. patent number 3,919,276 [Application Number 05/493,423] was granted by the patent office on 1975-11-11 for method of preparing amines and amides.
This patent grant is currently assigned to Dow Corning Corporation. Invention is credited to Gary E. Le Grow, John L. Speier.
United States Patent |
3,919,276 |
Le Grow , et al. |
November 11, 1975 |
Method of preparing amines and amides
Abstract
Amines and amides are prepared by reacting certain aliphatic,
cycloaliphatic and aromatic chlorides with N,N-substituted
triorganosilyl amines or N-substituted triorganosilyl amides. A
typical reaction is Me.sub.3 SiNMe.sub.2 + BuCl .fwdarw. Me.sub.3
SiCl + BuNMe.sub.2.
Inventors: |
Le Grow; Gary E. (Midland,
MI), Speier; John L. (Midland, MI) |
Assignee: |
Dow Corning Corporation
(Midland, MI)
|
Family
ID: |
23960168 |
Appl.
No.: |
05/493,423 |
Filed: |
July 31, 1974 |
Current U.S.
Class: |
556/413; 556/419;
564/215; 564/218; 564/305; 564/427; 564/463; 564/509; 556/469;
564/217; 564/222; 564/374; 564/462 |
Current CPC
Class: |
C07F
7/123 (20130101); C07C 209/08 (20130101); C07F
7/081 (20130101); C07F 7/1804 (20130101) |
Current International
Class: |
C07F
7/00 (20060101); C07F 7/18 (20060101); C07F
7/08 (20060101); C07F 7/12 (20060101); C07C
209/08 (20060101); C07C 209/00 (20060101); C07F
007/08 (); C07F 007/10 (); C07F 007/18 () |
Field of
Search: |
;260/448.2E,448.8R,561R,562R,578,583R |
References Cited
[Referenced By]
U.S. Patent Documents
Primary Examiner: Shaver; Paul F.
Attorney, Agent or Firm: Fleming, Jr.; Robert F.
Claims
That which is claimed is:
1. A method comprising reacting a compound of the formula (1 )
R.sub.3 SiNR'.sub.2 or R.sub.3 SiNHO=CR' with a chloride of the
formula (2 ) R"Cl at a temperature and pressure whereby compounds
of the formula R"NR'.sub.2 and R"NHO=CR' respectively are obtained
in which R and R' are alkyl groups and R" is a hydrocarbon radical
having no aliphatic carbon-carbon unsaturation beta to the chlorine
or a silyl substituted hydrocarbon radical of the formula X.sub.3
SiQ-- in which
X is alkyl, chlorine or alkoxy and
Q is a divalent hydrocarbon radical having no carbon-carbon
aliphatic unsaturation beta to the chlorine and of such size that
the chlorine is at least 3 carbon atoms removed from the
silicon.
2. A method in accordance with claim 1 in which (1 ) is a silyl
dialkyl amine and R" is X.sub.3 SiQ--.
3. A method in accordance with claim 1 in which (1) is a silyl
amide and in which R" is X.sub.3 SiQ--.
Description
It is known that N,N-substituted silyl amines will react with
activated halogen compounds to form amines and silicon halides.
Heretofore, however, this reaction has been suggested with only the
activated halogens such as acyl halides, chloro carbonates, alkyl
iodides, alpha-bromo ethers, benzyl chloride, carbon tetrachloride,
cyano-substituted halobenzenes and isocyanide dichlorides. As is
well known, such halogens are far more reactive than the chlorine
in, say, alkyl or aryl chlorides and it is, therefore, surprising
that this reaction will also go with the latter.
It is the object of this invention to provide a novel method for
the preparation of tertiary amines and of N-substituted amides.
This invention relates to a method comprising reacting a compound
of the formula R.sub.3 SiNR'.sub.2 or R.sub.3 SiNHO=CR' with a
chloride of the formula R"Cl at a temperature and pressure whereby
compounds of the formula R"NR'.sub.2 and R"NHO=CR' respectively are
obtained in which R and R' are alkyl groups and R" is a hydrocarbon
radical having no carbon-carbon aliphatic* unsaturation beta to the
chlorine or a silyl radical of the formula X.sub.3 SiQ-- in which X
is alkyl, chlorine or alkoxy and Q is a divalent hydrocarbon
radical having no carbon-carbon aliphatic unsaturation beta to the
chlorine and in which Q is of such size that the chlorine is at
least three carbon atoms removed from the silicon.
The advantages of the process of this invention are that no side
reactions occur giving rise to such compounds as quaternary
ammonium compounds, the by-produced triorganosilyl chloride is
easily removed from the reaction mixture and finally, no salt is
formed during this reaction. The latter is of particular importance
in this day of ecological problems since the disposal of amine
hydrochlorides can be quite serious.
The reaction of this invention is best carried out by heating a
mixture of the ingredients at a temperature of from 100.degree. to
250.degree.C. but below the decomposition of the product. With low
boiling reactants and products it is best to carry out the reaction
under autogenous pressure.
If desired, the reaction can be speeded up by using Lewis acid
catalysts such as aluminum chloride, ferric chloride or boron
trifluoride. In general, 1 percent by weight of the catalyst based
on the reactants is sufficient although more or less catalysts can
be used if desired.
For the purpose of this invention, R and R' can each be any alkyl
radical such as methyl, ethyl, isopropyl, octyl or dodecyl. X can
be any alkyl radical such as those shown for R or R' above and in
addition, any alkoxy group such as methoxy, ethoxy, isopropoxy,
butoxy or octadecyloxy.
R" can be any hydrocarbon radical in which there is no
carbon-carbon aliphatic unsaturation beta to the chlorine atom.
Thus, R" can be any alkyl radical such as methyl, ethyl, isopropyl,
octyl or octadecyl; alkenyl radicals such as 3-butenyl, 3-octenyl,
7-octadecenyl, 1-methyloctenyl-5, or 2-butyl-4-nonenyl; any
cycloaliphatic hydrocarbon radical such as cyclohexyl, cyclopentyl,
methylcyclohexyl, butylcyclohexyl, or 3-cyclohexene-1-yl; any
aromatic hydrocarbon radical such as phenyl, xenyl, naphthyl,
anthracyl, tolyl, or xylyl and any aralkyl radical such as
beta-phenylethyl, beta-naphthylethyl or omega-phenyloctyl.
Q can be any divalent hydrocarbon radical having no carbon-carbon
aliphatic unsaturation beta to the chlorine and being of such size
that there is at least three carbon atoms between the silicon and
the chlorine. Thus, Q can be alkylene radicals such as
trimethylene, tetramethylene, pentamethylene, or octadecamethylene
or any arylene radical such as phenylene, naphthylene,
anthracylene, or any cycloaliphatic hydrocarbon radical such as
cyclohexylene or methylcyclohexylene.
The following examples are illustrative only and should not be
construed as limiting the invention which is preperly delineated in
the appended claims.
EXAMPLE 1
An equimolar mixture of dimethylaminotrimethylsilane and n-butyl
chloride was placed in a sealed vessel. The vessel was heated at
165.degree.C. and the rate of the reaction was followed by
periodically taking samples and analyzing them by gas liquid
chromotography. Under these conditions, the reaction was 85 to 90
percent complete in 20.5 hours to give the product
butyldimethylamine.
The reaction was repeated except that 1 percent by weight aluminum
chloride based on the weight of the reactants was added. The
reaction was from 85 to 90 percent complete in 8 hours to produce
butyldimethylamine. The materials reacted at a constant rate of
about 0.17 moles per liter per hour without aluminum chloride and
about 0.4 moles per liter per hour with 1 percent aluminum
chloride.
EXAMPLE 2
An equimolar mixture of dimethylaminotrimethylsilane and n-pentyl
chloride containing 1 percent by weight aluminum chloride was
heated in a sealed vessel at 140 to 160.degree.C. for 18 hours. At
the end of this time gas liquid chromotography indicated a
quantitative yield of pentyl dimethyl amine.
EXAMPLE 3
The following chlorides were reacted with
dimethylaminotrimethylsilane in equimolar mixture in the presence
of 1 percent by weight of aluminum chloride in a sealed container
at 140.degree. to 160.degree.C. for 18 hours. The reaction
proceeded in accordance with the equation
R"Cl + Me.sub.3 SiNMe.sub.2 .fwdarw. Me.sub.3 SiCl + Me.sub.2
NR"
in which R" is as shown in the table below:
Percent Yield Structure of R" of Me.sub.2 NR"
______________________________________ phenyl 99%
1,1-dimethylpropyl 98% 2,2-dimethylpropyl 92% 1-methylbutyl 99%
beta-phenylethyl 99% gamma-(trimethoxysilyl)- 92% propyl
gamma-(trichlorosilyl)- 98% propyl para-(trichlorosilyl)- 93%
phenyl ______________________________________
EXAMPLE 4
The technique of Example 2 was repeated with a series of organic
chlorides and N-trimethylsilyl acetamide with 1 percent aluminum
chloride. The reaction proceeded according to the equation
R"Cl + CH.sub.3 C=ONHSiMe.sub.3 .fwdarw. Me.sub.3 SiCl + CH.sub.3
C=ONHR"
in which R" is as shown in the table below: Structure of R" Yield
of CH.sub.3 C=ONHR" ______________________________________ phenyl
94% gamma-(trichlorosilyl)- 96% propyl para-(trichlorosilyl)- 95%
phenyl gamma-(trimethoxysilyl)- 99% propyl 2,2-dimethylpropyl 99%
______________________________________
EXAMPLE 5
When the following silyl amines and silyl amides are reacted with
methyl chloride in accordance with the procedure of Example 1, the
following amines and amides are formed:
Silyl Amine Amine ______________________________________
isopropyldimethylsilyl- methyldibutyl- dibutylamine amine
octadecyldimethylsilyl- dimethylamine dimethylamine
trimethylsilylocta- octadecyldi- decylmethylamine methylamine Silyl
Amide Amide ______________________________________
N-isopropyldimethylsilyl N-methyl acetamide acetamide
N-trimethylsilyl valer- N-methyl valeramide amide
N-octadecyldimethylsilyl N-methyl acetamide acetamide
N-trimethylsilyl N-methyl stearamide stearamide
______________________________________
EXAMPLE 6
When trimethylsilyldimethylamine is reacted with the following
chlorides in accordance with the procedure of Example 1, the
following products are obtained.
______________________________________ Chloride Product
______________________________________ 3-octenyl chloride 3-octenyl
dimethyl amine octadecyl chloride octadecyldimethyl amine m-tolyl
chloride m-tolyldimethyl amine anthracyl chloride anthracyldimethyl
amine cyclohexyl chloride cyclohexyldimethyl amine Me.sub.3
SiCH=CH(CH.sub.2).sub.16 Cl Me.sub.3 SiCH=CH(CH.sub.2).sub.16
NMe.sub.2 C.sub.18 H.sub.37 Me.sub.2 SiCH.sub.2 CH.sub.2 Cl
C.sub.18 H.sub.37 Me.sub.2 SiCH.sub.2 CH.sub.2 NMe.sub.2 2
3-cyclohexenyl 3-cyclohexenyldimethyl chloride amine (C.sub.4
H.sub.9 O).sub.3 Si(CH.sub.2).sub.3 Cl (C.sub.4 H.sub.9 O).sub.3
Si(CH.sub.2).sub.3 NMe.sub.2
______________________________________
EXAMPLE 7
When the chlorides of Example 6 are reacted with N-trimethylsilyl
acetamide in accordance with the procedure of Example 4, the
following products are obtained:
N,3-octenyl acetamide
N-octadecyl acetamide
N,m-tolyl acetamide
N-anthracyl acetamide
N-cyclohexyl acetamide
Me.sub.3 SiCH=CH(CH.sub.2).sub.16 NHO=CMe ##EQU1## N,3-cyclohexenyl
acetamide (C.sub.4 H.sub.9 O).sub.3 Si(CH.sub.2).sub.3 NHO=CMe
* * * * *